WO2000007968A1 - Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands - Google Patents
Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands Download PDFInfo
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- WO2000007968A1 WO2000007968A1 PCT/US1999/017519 US9917519W WO0007968A1 WO 2000007968 A1 WO2000007968 A1 WO 2000007968A1 US 9917519 W US9917519 W US 9917519W WO 0007968 A1 WO0007968 A1 WO 0007968A1
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- formula
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- methyl
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- phenyl
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- 0 *c1c(CC(C(N)=O)O)cccc1 Chemical compound *c1c(CC(C(N)=O)O)cccc1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
- C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
- C07C13/465—Indenes; Completely or partially hydrogenated indenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Definitions
- Figure 1 illustrates a scheme for the synthesis of the Formula I compound, 2-methyl-7-chloroindene.
- Figure 2 is a NMR spectrum of 2-methyl-7- chloroindene produced by the Figure 2 scheme as shown by Example 1.
- Q is a hydrocarbyl group and X is a halogen, i.e., fluorine, chlorine, bromine or iodine.
- Q may be an alkyl group R x which may be any straight or branched chain alkyl group having 1 to 10 carbon atoms .
- Q may also be any aryl group Ar .
- Specific Ar groups include phenyl, napthyl and anthracyl groups . Phenyl and substituted phenyl groups are preferred. Substitution may be at any one or more available ring positions by an alkyl group, e.g., or by an aryl group or any other substituent including a halogen .
- X is the halogen substituent, preferably chlorine, of the Formula I compound.
- the Formula XV diester is saponified by heating, preferably in the presence of THF.
- the reaction mixture containing the diester is heated and combined with 30% to 60% aqueous alkali metal hydroxide MOH, preferably NaOH, to provide a compound having Formula V:
- the melt so produced is cooled to about 50°C, dissolved in a non-interfering solvent, e.g., an aliphatic hydrocarbon solvent having 6 to 9 carbon atoms, preferably heptane, and the Formula VII compound present in the solution is reacted with S0C1 2 at a temperature of 40 to 60°C with stirring to produce a Formula VIII compound:
- a non-interfering solvent e.g., an aliphatic hydrocarbon solvent having 6 to 9 carbon atoms, preferably heptane
- the acylation reaction is quenched by pouring on to ice.
- the layers which form are separated, and organic layer washed with an aqueous base, preferably sodium bicarbonate. All solvent is removed by distillation, methanol is added, and the reaction mixture containing Formula IX is cooled in an ice bath and combined with sodium borohydride to produce Formula X:
- a 5L round-bottom flask is equipped with a mechanical stirrer, thermometer and reflux condenser, and swept thoroughly with nitrogen.
- 2L tetrahydrofuran (THF) is added to the flask and then 116g NaH, 60% dispersion in mineral oil (2.9 mol) .
- An ice bath is applied to the flask and moderate stirring begun.
- 506g methyl diethyl malonate (2.9 mol) is added slowly from an addition funnel maintaining the temperature below 10°C. Hydrogen evolution is monitored and vented through a mineral oil bubbler and controlled by the rate of addition of the methyl dimethyl malonate. Once the addition is complete, the cooling bath is removed, and the reaction stirred for 2 hours.
- the reaction flask was allowed to cool to ambient temperature and 1.5L CH 2 C1 2 is added. Cooling was applied to -5° - 0°C, and 465g A1C1 3 (3.5 mol) added in portions . The reaction was stirred at ambient temperature for 2 hours , then quenched by pouring onto 2 Kg ice. The layers were separated, and the organic layer was washed with 500 mL H 2 0, and then 250 mL 5% w/v NaHC0 3 (aq) . All the solvent was distilled to a temperature of 70°C.
- the starting material for the Example 2 method for producing Formula I compounds is an alkali metal
- a carboxylic acid preferably a fatty acid, e.g., butanoic acid, having the Formula QCOOM (XII) in which Q and M are as defined.
- X is a halogen, preferably chlorine or bromine, i.e., the halogen of a Formula I compound.
- this series of reactions may be carried out by combining an alkali salt of Formula XII with an alkali metal diisopropylamide, preferably lithium diisopropylamide to produce a compound having the Formula XII in THF solution.
- the reaction is conducted at ambient temperature and preferably stirred for 24 hours.
- 2-halo benzylhalide is added to the reaction mixture so produced, and the reaction mixture stirred for an additional time period, preferably 18 to 24 hours.
- the reaction is then quenched, e.g., by the addition of water.
- the aqueous layer is neutralized by a mineral acid, e.g., hydrochloric acid, at which point a phase separation occurs.
- a 2- halobenzyl fatty acid such as the compound of Formula XIII, is concentrated in the organic layer.
- a 12L round-bottom flask was equipped with a mechanical stirrer, thermometer and reflux condenser.
- Formula II compounds are prepared in known manner by reacting a Formula I compound with a Grignard reagent, ArMgX, in which X is as described, preferably Br and Ar is as described, in an ethyl ether solvent containing 1-3-bis (diphenylphosphino) propane nickel II chloride, Ni (dpp) .
- Examples 3-6 utilize the synthesis of the Formula II compounds depicted by Figure 4.
- EXAMPLE 3 A 5L round bottom flask was equipped with mechanical stirring, a reflux condenser and ice bath. 488.2g distilled 7-chloro-2-methylindene (2.97 mol) was added, dissolved in 2L ether and 32.2g Ni (dpp) (0.059 mol, 2 mol%) slurried in the solution, and stirred to cool to 0- 2°C. 1.05L of 3.1M phenylmagnesium bromide in ether (3.25 mol, 10% excess) was added slowly from an addition funnel so that the temperature remained below 5°C. Once complete, the ice bath was removed, and the reaction stirred up to room temperature. The reaction was refluxed for 8 hours , and checked for completion by GC .
- EXAMPLE 3(a) 2-phenyl-7 phenyl indene is prepared in like manner from 2-phenyl 7 chloroindene as produced by Example 1(a) .
- EXAMPLE 4 A 12L flask equipped as in Example 3 was charged with 661g distilled 2-methyl-7-chloroindene (4 mol), 2.5L ether, and 43.3g Ni (dpp) (0.08 mol, 2 mol%) . 1.75L of 2.6M phenylmagnesium bromide in ether (4.55 mol, 12% excess) was added at 2°C. Following stir-out to ambient temperature and reflux for 8 hours , the reaction was quenched and worked up by the method described in Example 3. Yield of 2-methyl-7-phenylindene (same as 2- methyl- -phenylindene) was 642.7g (3.12 mol) equal to 78%,
- EXAMPLE 5 A 5L flask was equipped as in Example 3. 178g 2- ethyl-7-chloroindene (1 mol), IL ether and 10.8g Ni (dpp) (0.02 mol, 2 mol%) added, followed by 355 mL of 3.1M phenylmagnesium bromide in ether (1.1 mol, 10% excess) . A ter quenching and work-up by the method described in Example 3, 176g 2-ethyl-7-phenylindene (0.8 mol) was obtained by vacuum distillation at 140°C in 80% yield.
- EXAMPLE 5(a) 2-phenyl-7-napthylindene is prepared in like manner from 2-phenyl-7- ⁇ hloroindene (see Example 1(a)) and naphthyl magnesium bromide .
- EXAMPLE 6 A 5L flask was equipped as described in Example 3. 164g 2-methyl-7-chloroindene (1 mol) 500 mL ether and 10.8g Ni(dpp) added. 2L of 0.5M naphthyl magnesium bromide in ether was added at 20°C. The reaction was stirred vigorously at reflux for 12 hours , then quenched and worked up as described in Example 3. 184.3g 2-me hy1- 7- (1-naphthyl) indene (Spaleck compound 21) (0.72 mol) was obtained by recrystallization from heptane in 72% yield.
- L is -SiY 2 - in which Y is an alkyl group preferably having 1 to 5 carbon atoms or - (CH 2 ) n - in which n is 1 to 4 atoms, M 2 is Zr, Hf or Ti and X is a halogen, preferably chlorine.
- -SiY 2 - is preferably -(CH 3 ) 2 Si- and MaXj is preferably ZrCl 2 .
- Example 7 illustrates one such conversion.
- the reaction mixture was then filtered and the solids were washed with hexane.
- the solids were dried under vacuum.
- the dry solids were dissolved in dichloromethane (800 mL) and this solution filtered through a small bed of celite to remove lithium chloride. The volume was reduced to 100 mL by solvent removal.
- the filtered crystals were washed with 10-15 mL dichloromethane and then dried in vacuum. The retained yield—60-80g 2 methyl-7-naphthy1- indene-Si (CH 3 ) 2 7-napthyl-2-methyl indene.
- 2-aryl-4-aryl ansa metallocenes may be prepared.
- Such metallocenes may include 2-phenyl-7- phenylindene Si (CH 3 ) 2 -7-phenyl-2-phenylindene .
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000563603A JP2002522405A (en) | 1998-08-03 | 1999-08-03 | Coupling reaction of 2-substituted, 7-haloindene with aryl substituents to form metallocene catalyzed ligands |
EP99938949A EP1027314A4 (en) | 1998-08-03 | 1999-08-03 | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands |
AU53324/99A AU764843B2 (en) | 1998-08-03 | 1999-08-03 | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands |
NZ503655A NZ503655A (en) | 1998-08-03 | 1999-08-03 | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands |
CA002305363A CA2305363A1 (en) | 1998-08-03 | 1999-08-03 | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/127,796 US6465700B1 (en) | 1997-02-05 | 1998-08-03 | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands |
US09/127,796 | 1998-08-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000007968A1 true WO2000007968A1 (en) | 2000-02-17 |
Family
ID=22431994
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/017519 WO2000007968A1 (en) | 1998-08-03 | 1999-08-03 | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands |
Country Status (7)
Country | Link |
---|---|
US (1) | US6465700B1 (en) |
EP (1) | EP1027314A4 (en) |
JP (1) | JP2002522405A (en) |
AU (1) | AU764843B2 (en) |
CA (1) | CA2305363A1 (en) |
NZ (1) | NZ503655A (en) |
WO (1) | WO2000007968A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001085649A2 (en) * | 2000-05-08 | 2001-11-15 | Boulder Scientific Company | Synthesis of 2-halobenzyl alkanoic acid |
WO2003084904A1 (en) * | 2002-04-10 | 2003-10-16 | Basell Polyolefine Gmbh | Preparation of substituted indenes |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
JP2005255561A (en) * | 2004-03-09 | 2005-09-22 | Kyoto Univ | Multi-substituted pyrimidine and method for selectively producing the same |
WO2006065844A2 (en) * | 2004-12-16 | 2006-06-22 | Exxonmobil Chemical Patents Inc. | Process for producing substituted metallocene compounds for olefin polymerization |
US7667064B2 (en) * | 2005-12-14 | 2010-02-23 | Exxonmobil Chemical Patents Inc. | Halogen substituted metallocene compounds for olefin polymerization |
US7868197B2 (en) | 2005-12-14 | 2011-01-11 | Exxonmobil Chemical Patents Inc. | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US7763562B2 (en) * | 2005-12-14 | 2010-07-27 | Exxonmobil Chemical Patents Inc. | Heteroatom bridged metallocene compounds for olefin polymerization |
US7550544B2 (en) | 2005-12-14 | 2009-06-23 | Exxonmobil Chemical Patents Inc. | Halogen substituted metallocene compounds for olefin polymerization |
US7538168B2 (en) | 2005-12-14 | 2009-05-26 | Exxonmobil Chemical Patents Inc. | Halogen substituted metallocene compounds for olefin polymerization |
US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
JP2010529253A (en) | 2007-06-04 | 2010-08-26 | エクソンモービル・ケミカル・パテンツ・インク | Very homogeneous solution polymerization of propylene |
US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
US7812104B2 (en) * | 2008-01-18 | 2010-10-12 | Exxonmobil Chemical Patents Inc. | Production of propylene-based polymers |
ES2367489B1 (en) | 2008-04-04 | 2012-09-07 | Rothenberger, S.A. | MANUAL DRIVE CURVATUBES. |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2953609A (en) * | 1958-04-29 | 1960-09-20 | American Oil Co | Preparation of substituted tetrahydro-indenoindene |
US4219687A (en) * | 1978-07-26 | 1980-08-26 | Standard Oil Company | Hydroalkylation of benzene and analogs |
US5602228A (en) * | 1995-06-06 | 1997-02-11 | Maxdem Incorporated | Nickel phosphate catalysts |
US5936108A (en) * | 1996-10-17 | 1999-08-10 | Albemarle Corporation | Metallocene synthesis |
US5965759A (en) * | 1998-09-23 | 1999-10-12 | Albemarle Corporation | Catalytic process for isomerizing metallocenes |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW294669B (en) * | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
AU5299493A (en) * | 1992-10-19 | 1994-05-09 | E.I. Du Pont De Nemours And Company | Arthropodicidal semicarbazones |
US5789634A (en) * | 1997-02-05 | 1998-08-04 | Boulder Scientific Company | Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst intermediates |
-
1998
- 1998-08-03 US US09/127,796 patent/US6465700B1/en not_active Expired - Lifetime
-
1999
- 1999-08-03 CA CA002305363A patent/CA2305363A1/en not_active Abandoned
- 1999-08-03 EP EP99938949A patent/EP1027314A4/en not_active Withdrawn
- 1999-08-03 AU AU53324/99A patent/AU764843B2/en not_active Ceased
- 1999-08-03 JP JP2000563603A patent/JP2002522405A/en active Pending
- 1999-08-03 NZ NZ503655A patent/NZ503655A/en not_active IP Right Cessation
- 1999-08-03 WO PCT/US1999/017519 patent/WO2000007968A1/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2953609A (en) * | 1958-04-29 | 1960-09-20 | American Oil Co | Preparation of substituted tetrahydro-indenoindene |
US4219687A (en) * | 1978-07-26 | 1980-08-26 | Standard Oil Company | Hydroalkylation of benzene and analogs |
US5602228A (en) * | 1995-06-06 | 1997-02-11 | Maxdem Incorporated | Nickel phosphate catalysts |
US5936108A (en) * | 1996-10-17 | 1999-08-10 | Albemarle Corporation | Metallocene synthesis |
US5965759A (en) * | 1998-09-23 | 1999-10-12 | Albemarle Corporation | Catalytic process for isomerizing metallocenes |
Non-Patent Citations (1)
Title |
---|
See also references of EP1027314A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001085649A2 (en) * | 2000-05-08 | 2001-11-15 | Boulder Scientific Company | Synthesis of 2-halobenzyl alkanoic acid |
WO2001085649A3 (en) * | 2000-05-08 | 2002-03-21 | Boulder Scient Co | Synthesis of 2-halobenzyl alkanoic acid |
WO2003084904A1 (en) * | 2002-04-10 | 2003-10-16 | Basell Polyolefine Gmbh | Preparation of substituted indenes |
Also Published As
Publication number | Publication date |
---|---|
JP2002522405A (en) | 2002-07-23 |
EP1027314A4 (en) | 2003-03-19 |
AU5332499A (en) | 2000-02-28 |
AU764843B2 (en) | 2003-09-04 |
EP1027314A1 (en) | 2000-08-16 |
CA2305363A1 (en) | 2000-02-17 |
US6465700B1 (en) | 2002-10-15 |
NZ503655A (en) | 2001-09-28 |
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